CN103814310B - Heat ray shielding material - Google Patents
Heat ray shielding material Download PDFInfo
- Publication number
- CN103814310B CN103814310B CN201280045500.6A CN201280045500A CN103814310B CN 103814310 B CN103814310 B CN 103814310B CN 201280045500 A CN201280045500 A CN 201280045500A CN 103814310 B CN103814310 B CN 103814310B
- Authority
- CN
- China
- Prior art keywords
- metallic particles
- layer
- ray shielding
- heat ray
- shielding material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- G—PHYSICS
- G02—OPTICS
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Abstract
The present invention relates to a kind of heat ray shielding material, described heat ray shielding material is characterised in that, its metallic particles with the metallic particles comprising at least one type comprises layer, wherein, the thickness that described metallic particles comprises layer is 10nm��80nm, the hexagon that described metallic particles comprises at least 60 number % is to circular dull and stereotyped shape metallic particles, and described hexagon to the mean thickness of circular dull and stereotyped shape metallic particles is no more than 14nm. Described heat ray shielding material has favourable visible light transmissivity, thermal shielding capability (solar reflectance), surface topography and scratch resistance.
Description
Technical field
The present invention relates to a kind of heat ray shielding material, this heat ray shielding material has good visible light permeability, thermal shielding capability and scratch resistance.
Background technology
In recent years, as one of conservation measures cutting down carbonic acid gas, develop the material that the window of vehicle or buildings can be given heat ray shielding ability. From the angle of heat ray shielding ability (the hot acquisition rate of solar radiation), required is without the heat-reflective radiated again, and non-absorbing is radiated the thermal absorption type of indoor (the absorption solar radiant energy of about 1/3) again, this is proposed various scheme.
As filter for shielding infrared ray, the spectral filter (see patent documentation 1) of the flat plate-like particles of Ag is proposed to use. But, filter for shielding infrared ray owing to describing in patent documentation 1 is intended to for plasma display (PDP), and do not carry out orecontrolling factor due to this kind of Ag plate-like particles, therefore this spectral filter mainly plays the infrared ray absorption function in infrared rays district, and can not be used as initiatively to reflect the material of invisible heat. Therefore, when being used for shielding direct sunlight by the filter for shielding infrared ray comprising this kind of flat plate-like particles of Ag, IR absorption filter itself will heat up, and raise envrionment temperature because of its heat, and thus it is not enough as the function of infrared shield material. In the embodiment of patent documentation 1, the dispersion liquid comprising the flat plate-like particles of Ag is applied on glass and drying thereon, thus filter for shielding infrared ray is provided; But, it is 1 ��m that the document describes the thickness of desciccator diaphragm, i.e. 1000nm.
Patent documentation 2 describes the wavelength selectivity film using granular silver. In patent documentation 2, the Ag layer being distributed with granular Argent grain is formed by sputtering Ag and thermal treatment; As shown in Fig. 3 of the document, multiple granular Argent grain has irregular shape. In addition, in the embodiment of patent documentation 2, the thickness of the Ag layer formed has the thickness of 5mm, but it does not describe the content about relation between Argent grain thickness and Ag layer thickness.
Patent documentation 3 describes a kind of solar energy shielding film, and it is provided with the hard coat giving near-infrared shielding function between bonding coat and substrate. Patent documentation 3 only describes and uses near-infrared-absorbing material to carry out the enforcement mode that hard coat is given near-infrared shielding function, and but, this hard coat can not be used as initiatively to reflect the material of invisible heat. Therefore, when the filter for shielding infrared ray using this kind to comprise the flat plate-like particles of Ag is to shield direct sunlight, then infrared absorbing filter itself will be heated, and improve envrionment temperature due to its heat, and thus it is as the function deficiency of infrared shield material.In addition, patent documentation 3 discloses organic near infrared ray absorption and inorganic near infrared ray absorption as near-infrared-absorbing material, in other words, this document describe the enforcement mode using metallic particles, but not about the shape of this metallic particles and any record of thickness. In addition, the thickness that the document describes hard coat is generally 1 ��m��10 ��m, i.e. 1000nm��10000nm.
On the other hand, patent documentation 4 discloses a kind of heat ray shielding material, it has hexagon that ratio is at least 60 number % to circular plate metallic particles, wherein, the surface that described hexagon to the principal plane of circular plate metallic particles comprises layer relative to metallic particles is average 0 �㡫�� 30 �� of scope inner plane orientations. Patent documentation 4 does not describe the preferable range that metallic particles comprises the thickness of layer, and in its embodiment, and only disclosing metallic particles, to comprise layer be 0.1 ��m��0.5 ��m, i.e. the enforcement mode of 100nm��500nm.
Quote list
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-178915 publication
Patent documentation 2: Japanese Patent No. 3454422 publications
Patent documentation 3: Japanese Unexamined Patent Publication 2008-248131 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-118347 publication
Summary of the invention
Technical problem
The research that the present inventor makes shows, in patent documentation 1 describe filter for shielding infrared ray and patent documentation 3 in describe solar energy reflection film be infrared ray absorption type, therefore, when they are for shielding daylight heat, infrared absorbent itself is heated thus raises envrionment temperature. In addition, when they adhere to pane, then there will be another problem: glass is due to the part by sun exposure with not by the rise in temperature difference between the part of sun exposure break (hot tearing).
In patent documentation 2, when using granular elecscreen to cover infrared rays, then can not be sharp keen owing to the half breadth of spectrum is relatively big shield infrared rays, that is, there is the problem that film can not shield shortwave side infrared rays (it has a large amount of solar energy) completely.
In patent documentation 4 describe heat ray shielding material can reflect red outside line, thus can advantageously as infrared shield film. But, present inventors studied in patent documentation 4 invention described, and find its point defect that there is the shrinkage cavity shape that size (i.e. diameter) is more than 0.1mm. In addition, in the invention described in patent documentation 4, when reducing the thickness of Ag containing layer to prevent during above-mentioned point defect, then there is the problem that dull and stereotyped shape metallic particles easily peels off when frictional metal particle comprises layer.
The present invention is just in order to solve the problem. Specifically, the technical problem that the present invention is directed to is to provide a kind of heat ray shielding material, and it has good visible light permeability, thermal shielding capability (solar reflectance), surface topography and rub resistance.
Technical scheme
In order to solve the problem, the present inventor makes lucubrate, found that, when the shape of dull and stereotyped shape metallic particles is too random, then heat ray shielding is less able. In addition, the present inventor also finds, in the formation of patent documentation 4, when reducing, in order to increase heat ray shielding ability, the thickness that metallic particles comprises layer, then due to the problem of above-mentioned rub, dull and stereotyped shape metallic particles will peel off or it constructs entanglement, thus can not obtain stable heat ray shielding function.
In view of this, the metallic particles that the present inventor attempts in the formation of reduction patent documentation 4 comprises the thickness of layer, also reduce the thickness that dull and stereotyped shape metallic particles comprises the flat plate-like particles in layer with specified shape simultaneously, and successfully provide a kind of heat ray shielding material with good visible light permeability, thermal shielding capability (solar reflectance), surface topography and rub resistance at this.
The above-mentioned discovery that the present invention makes based on contriver, and for the scheme that solves the problems of the technologies described above as follows described in:
[1] a kind of heat ray shielding material, the metallic particles that described heat ray shielding material has the metallic particles comprising at least one type comprises layer, wherein, the thickness that described metallic particles comprises layer is 10nm��80nm, described metallic particles is to comprise hexagon to circular dull and stereotyped shape metallic particles relative to the total quantity of described metallic particles as the ratio of at least 60 number %, and described hexagon to the mean thickness of circular dull and stereotyped shape metallic particles is 14nm at the most.
[2] preferably, in the heat ray shielding material described in [1], the coefficient of variation of leveled circular equivalent diameter is at the most 30%.
[3] preferably, in the heat ray shielding material described in [1] or [2], leveled circular equivalent diameter is 70nm��500nm, and aspect ratio (average particulate diameter/average particle thickness) is 6��40.
[4] preferably, in [1]��[3] in heat ray shielding material described in either side, described hexagon at least comprises silver to circular dull and stereotyped shape metallic particles.
[5] preferably, in [1]��[4] in heat ray shielding material described in either side, described hexagon to the principal plane of circular dull and stereotyped shape metallic particles comprises a surface of layer average 0 �㡫�� 30 �� of scope inner plane orientations relative to described metallic particles.
[6] preferably, in [1]��[5] in heat ray shielding material described in either side, described metallic particles comprises layer and comprises polymkeric substance.
[7] preferably, in [1]��[6] in heat ray shielding material described in either side, the principal polymeric that described metal comprises the described polymkeric substance comprised in layer is vibrin.
[8] preferably, in [1]��[7], heat ray shielding material described in either side has the layer comprising UV light absorber.
[9] preferably, the heat ray shielding material described in [8] aspect has bonding coat, and wherein, the layer that described bonding coat or described bonding coat and described metallic particles comprise between layer comprises UV light absorber.
[10] preferably, in [1]��[9], the visible light transmissivity of heat ray shielding material described in either side is at least 70%.
[11] preferably, heat ray shielding material reflect red outside line described in either side in [1]��[10].
Technique effect
According to the present invention, it provides a kind of heat ray shielding material, described shielding material has good visible light permeability, thermal shielding capability (solar reflectance), surface topography and rub resistance.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is the schematic diagram of an example of the invisible heat masking material of display the present invention.
[Fig. 2] Fig. 2 is the schematic diagram of another example of the invisible heat masking material of display the present invention.
[Fig. 3 A] Fig. 3 A is the schematic diagram of another example of the invisible heat masking material of display the present invention.
[Fig. 3 B] Fig. 3 B is the schematic diagram of another example of the invisible heat masking material of display the present invention.
[Fig. 3 C] Fig. 3 C is the schematic diagram of another example of the invisible heat masking material of display the present invention.
[Fig. 4 A] Fig. 4 A is the perspective illustration of an example of the shape of the flat plate-like particles contained in the invisible heat masking material of display the present invention, and shows circular dull and stereotyped shape metallic particles.
[Fig. 4 B] Fig. 4 B is the perspective illustration of an example of the shape of the flat plate-like particles contained in the invisible heat masking material of display the present invention, and shows hexagonal dull and stereotyped shape metallic particles.
[Fig. 5 A] Fig. 5 A be display the present invention invisible heat masking material in metallic particles containing dull and stereotyped shape metallic particles comprise the schematic sectional view of existence of layer, and illustrate the metallic particles containing dull and stereotyped shape metallic particles and comprise the angle (��) between layer (and plane parallel of base material) and the principal plane (it determines equivalent circle diameter D) of flat board shape metallic particles.
[Fig. 5 B] Fig. 5 B be display the present invention invisible heat masking material in metallic particles containing dull and stereotyped shape metallic particles comprise the schematic sectional view of existence of layer, and show metallic particles and comprise in layer the domain of the existence at the depth direction upper flat plate shape metallic particles of invisible heat masking material.
[Fig. 5 C] Fig. 5 C is the schematic sectional view that the metallic particles containing dull and stereotyped shape metallic particles in the invisible heat masking material of display the present invention comprises an example of the existence of layer.
[Fig. 5 D] Fig. 5 D is the schematic sectional view that the metallic particles containing dull and stereotyped shape metallic particles in the invisible heat masking material of display the present invention comprises another example of the existence of layer.
[Fig. 5 E] Fig. 5 E is the schematic sectional view that the metallic particles containing dull and stereotyped shape metallic particles in the invisible heat masking material of display the present invention comprises another example of the existence of layer.
Embodiment
The heat ray shielding material of the present invention will be described below in detail.
The description to integrant of the present invention hereafter provided is only in order to describe the part exemplary embodiment of the present invention, but the present invention is not limited to this. In this manual, the numerical range expressed by phrase " a certain numeral��another numeral " represents the scope fallen between a front numeral (representing the lower limit of this scope) and a rear numeral (representing the upper limit of this scope).
(heat ray shielding material)
The metallic particles that the heat ray shielding material of the present invention has the metallic particles comprising at least one type comprises layer, wherein, the thickness that described metallic particles comprises layer is 10nm��80nm, described metallic particles is to comprise hexagon to circular dull and stereotyped shape metallic particles relative to the sum of described metallic particles as the ratio of at least 60 number %, and described hexagon to the mean thickness of circular dull and stereotyped shape metallic particles is 14nm at the most.
In one preferred embodiment, the metallic particles that the heat ray shielding material of the present invention has the metallic particles comprising at least one type comprises layer, and selection of land can have any other layer, as bonding coat, UV-absorbing layer, plaque layer, metal oxide particle comprise layer etc.
Layer about heat ray shielding material constructs, enforcement mode as shown in Figure 1 can be mentioned, the metallic particles that wherein heat ray shielding material 10 has a metallic particles comprising at least one type comprises layer 2, and wherein, dull and stereotyped shape metallic particles 3 is arranged in the surface of this layer in off-centered mode. Can also mentioning enforcement mode as shown in Figure 2, wherein this material has metallic particles and comprises layer 2 and be positioned at the top coating 4 that this metallic particles comprises on layer, and its middle plateform shape metallic particles 3 is arranged in, in off-centered mode, the surface that metallic particles comprises layer.
In addition, it is advantageous that, mention enforcement mode as shown in Figure 3A, wherein this material has substrate 1, the metallic particles that is positioned on substrate comprises layer 2 and be positioned at the bonding coat 11 that metallic particles comprises on layer.
It is further advantageous that mention enforcement mode as shown in Figure 3 B, wherein this material has substrate 1, the metallic particles that is positioned on substrate comprises layer 2, be positioned at metallic particles comprises on layer top coating 4 and the bonding coat 11 being positioned in the coating of top.In the heat ray shielding material of the present invention shown in Fig. 3 A or 3B, it is preferred that top coating 4 or bonding coat 11 comprise UV light absorber.
It is further advantageous that mention enforcement mode as shown in Figure 3 C, wherein this material has hard coat 5, and the metallic particles that has that this hard coat 5 is positioned at substrate 1 comprises on the opposition side of layer 2 side.
<1. metallic particles comprises layer>
Metallic particles comprises the layer that layer is the metallic particles comprising at least one type, it suitably can be selected and do not limit according to predetermined object, if metallic particles wherein taking relative to the sum of metallic particles as the ratio of at least 60 number % comprise hexagon to circular dull and stereotyped shape metallic particles and hexagon to the mean thickness of circular dull and stereotyped shape metallic particles for 14nm at the most.
When the thickness that metallic particles is comprised layer is called d, desirably the hexagon of at least 80 number % to circular dull and stereotyped shape metallic particles is present in from the surface that metallic particles comprises layer in the scope of its d/2 degree of depth, it is more preferable to be present in from the surface that metallic particles comprises layer in the scope of its d/3 degree of depth. Being not limited to any theory, the heat ray shielding material of the present invention is not limited to according to the material that following preparation method obtains; But, when forming metallic particles and comprise layer, by adding specific polymkeric substance (being preferably latex) wherein, and dull and stereotyped shape metallic particles is made to be arranged in, in off-centered mode, the surface that metallic particles comprises layer.
1-1. metallic particles
It is not particularly limited, metallic particles suitably can be selected according to predetermined object, condition is metallic particles to comprise hexagon to circular dull and stereotyped shape metallic particles relative to the sum of metallic particles as the ratio of at least 60 number %, and wherein hexagon to the mean thickness of circular dull and stereotyped shape metallic particles is 14nm at the most.
The existence form in layer is comprised at metallic particles about hexagon to circular dull and stereotyped shape metallic particles, desirably, dull and stereotyped shape metallic particles comprises a surface (when the heat ray shielding material of the present invention has substrate, relative to substrate surface) of layer average 0 �㡫�� 30 �� of scope inner plane orientations relative to metallic particles.
Preferably, the surface that metallic particles comprises layer is flat surfaces. When the metallic particles of the heat ray shielding material of the present invention comprise layer have substrate serve as interim support, it is desirable to, the surface on surface and substrate that metallic particles comprises layer is all the surface close to level. Herein, heat ray shielding material can have or not have interim support.
Being not particularly limited, the size of metallic particles suitably can be selected according to predetermined object. Such as, the median size of particle can be 500nm at the most.
Also being not particularly limited, the material of metallic particles suitably can be selected according to predetermined object. From the angle that its invisible heat (near infrared ray) reflectivity is higher, it is preferred that silver, gold, aluminium, copper, rhodium, nickel, platinum etc.
The dull and stereotyped shape metallic particles of 1-2.
Being not particularly limited, dull and stereotyped shape metallic particles suitably can be selected according to predetermined object, as long as it is the particle (see Fig. 4 A and Fig. 4 B) of each self-contained two principal planes. Such as, hexagon, circle, trilateral etc. can be mentioned. Wherein, from the angle of high visible light transmissivity, it is more preferable to be that the Polygons of more than hexagon is to circular. More preferably hexagon or circle.
In this manual, circle refers to following shape: in following metal plate shape particle (its implication is identical with dull and stereotyped shape metallic particles), ignore particle average equivalent circular diameter at the most 10% surfaceness time, in each dull and stereotyped shape metallic particles length be average equivalent circular diameter at the most 50% the number of side be 0 (zero).Circular dull and stereotyped shape metallic particles is not particularly limited, it is possible to suitably select according to predetermined object, and condition is that this particle does not have angle and has round wheel shape when shape metallic particles dull and stereotyped from its principal plane top view with transmission electron microscope (TEM).
In this manual, hexagon refers to following shape: ignore following dull and stereotyped shape metallic particles average equivalent circular diameter at the most 10% surfaceness time, in each dull and stereotyped shape metallic particles length be average equivalent circular diameter at the most 20% the number of side be 6. Other Polygonss can also define equally. Hexagonal dull and stereotyped shape metallic particles is not particularly limited, it is possible to suitably select according to predetermined object, and condition is that this particle has hexagon shape when shape metallic particles dull and stereotyped from its principal plane top view with transmission electron microscope (TEM). Such as, the angle of hexagon particle can be acute angle or obtuse angle. But, the angle of the ability of visible absorption is reduced from particle, it is preferred that angle is obtuse angle. Obtuse angle angle is not particularly limited, it is possible to suitably select according to predetermined object.
Being not particularly limited, dull and stereotyped shape metallic particles can be identical with aforementioned metal particle, and suitably selects according to predetermined object. Preferably, dull and stereotyped shape metallic particles at least comprises silver.
Comprising in layer at metallic particles in the metallic particles existed, relative to the sum of metallic particles, described hexagon is at least 60 number % to the ratio of circular dull and stereotyped shape metallic particles, it is preferable that at least 65 number %, it is more preferable at least 70 number %. When the ratio of dull and stereotyped shape metallic particles is less than 60 number %, then the visible light transmissivity of this layer may reduce.
1-2-1. planar orientation
Preferably, in the heat ray shielding material of the present invention, the surface that hexagon to the principal plane of circular dull and stereotyped shape metallic particles comprises layer relative to metallic particles is (when heat ray shielding material has substrate, then relative to the surface of substrate) the average 0 �㡫�� scope inner plane orientation of 30 ��, more preferably in the average 0 �㡫�� scope of 20 ��, also more preferably in the average 0 �㡫�� scope of 5 ��.
Being not particularly limited, the existence of dull and stereotyped shape metallic particles suitably can be selected according to predetermined object, but, it is preferred that this particle arranges as shown in following Fig. 5 D or Fig. 5 E.
Herein, the metallic particles that Fig. 5 A��Fig. 5 E comprises dull and stereotyped shape metallic particles for illustrating in the heat ray shielding material of the present invention separately comprises the schematic sectional view of the existence of layer. Fig. 5 C, Fig. 5 D and Fig. 5 E each illustrate dull and stereotyped shape metallic particles 3 and comprise the existence in layer 2 at metallic particles. Fig. 5 A is the view that the angle (�� ��) formed between the plane of substrate 1 and the principal plane (it determines equivalent circle diameter D) of dull and stereotyped shape metallic particles 3 is described. Fig. 5 B shows metallic particles and comprises the domain of the existence of layer 2 along the depth direction of heat ray shielding material.
In fig. 5, angle (�� ��) between the surface of substrate 1 and the principal plane of dull and stereotyped shape metallic particles 3 or principal plane extended line is corresponding to the pre-determined range of above-mentioned planar orientation. Specifically, planar orientation refers to that the pitch angle (�� ��) shown in Fig. 5 A is less when observing the cross section of heat ray shielding material; Particularly, as shown in Figure 5 D, planar orientation refers to that the surface of substrate 1 and the principal plane of dull and stereotyped shape metallic particles 3 keep in touch, or in other words, �� is 0 ��. When dull and stereotyped shape metallic particles 3 principal plane relative to the planar orientation angle (i.e. �� in Fig. 5 A) on the surface of substrate 1 be greater than �� 30 �� time, such as, then the reflectivity of the predetermined wavelength (from visible wavelength side to near-infrared region) of heat ray shielding material will reduce.
It is not particularly limited, the evaluation of a surface (when heat ray shielding material has substrate, then relative to the surface of the substrate) the planar orientation whether principal plane of dull and stereotyped shape metallic particles comprises layer relative to metallic particles suitably can be selected according to object. Such as, in a kind of evaluation method that can adopt herein, such as, preparing the suitable cut-plane slices of heat ray shielding material, the metallic particles observed in this section comprises layer (being substrate when heat ray shielding material comprises substrate) peace plate-shape metal particle and evaluates. Specifically, micro-slicing machine or focused ion beam technology (FIB) is used to cut heat ray shielding material, to prepare section sample or cut-plane slices sample, with various microscope (such as, field emission scanning electron microscope (FE-SEM) etc.) etc. observe sample, analyze gained image to carry out predetermined evaluation.
In heat ray shielding material, when the tackiness agent of coated dull and stereotyped shape metallic particles expands in water, then can cut the heat ray shielding material sample through liquid nitrogen freezing with the use of the diamond cutting knife being arranged on micro-slicing machine, thus obtained section sample or cut-plane slices sample. On the other hand, when the tackiness agent of coated dull and stereotyped shape metallic particles does not expand in water, it is possible to directly obtain desired section sample or cut-plane slices sample from this material.
It is not particularly limited, the section sample obtained with upper type or cut-plane slices sample can be observed in any mode suitably selected according to predetermined object, as long as can confirm that whether the principal plane of sample middle plateform shape metallic particles comprises a surface (being the surface of substrate when heat ray shielding material the has substrate) planar orientation of layer relative to metallic particles. Such as, it can be mentioned use FE-SEM, TEM and opticmicroscope etc. to observe. Section sample can utilize FE-SEM to observe, and cut-plane slices sample can utilize tem observation. When utilizing FE-SEM to evaluate, it is desirable to, this microscope has the spatial resolving power at the shape that can clearly determine dull and stereotyped shape metallic particles and pitch angle (in Fig. 5 A �� ��).
The size distribution of 1-2-2. median size (leveled circular equivalent diameter) and median size (leveled circular equivalent diameter)
Being not particularly limited, the median size (leveled circular equivalent diameter) of dull and stereotyped shape metallic particles suitably can be selected according to predetermined object. Preferably, median size is 70nm��500nm, it is more preferable to be 100nm��400nm. When median size (leveled circular equivalent diameter) is less than 70nm, then the contribution absorbed will be greater than particle to the contribution of reflection by dull and stereotyped shape metallic particles, and therefore, this material can not guarantee enough invisible heat reflectivity; But, when more than 500nm, then mist degree (scattering) will become big so that the transparency of substrate thus declines.
The statistical average of the principal plane diameter (maximum length) of random 200 the flat plate-like particles selected the image that median size (leveled circular equivalent diameter) obtains when referring to and observe from TEM image.
Metallic particles comprises layer can comprise the different two or more different metallic particles of median size (leveled circular equivalent diameter); In this case, metallic particles can have the peak of the two or more of median size (leveled circular equivalent diameter), and namely metallic particles can have two or more median sizes (leveled circular equivalent diameter).
In the heat ray shielding material of the present invention, it is preferred that the coefficient of variation of the size distribution of dull and stereotyped shape metallic particles is at the most 30%, it is more preferable to be at the most 20%.When coefficient of variation is greater than 30%, then the invisible heat reflected wavelength range of heat ray shielding material becomes wide.
Herein, the coefficient of variation of the size distribution of dull and stereotyped shape metallic particles is calculated value (%), the calculated value (%) such as calculated in the following manner: to the standard deviation of the particle size distribution range mapping for the dull and stereotyped shape metallic particles that calculates 200 of above-mentioned mean value to determine size distribution, with its mean value (median size (leveled circular equivalent diameter)) divided by the principal plane diameter (maximum length) as above obtained, obtain required value (%).
The thickness of the dull and stereotyped shape metallic particles of 1-2-3. and aspect ratio
In the heat ray shielding material of the present invention, the thickness of dull and stereotyped shape metallic particles is 14nm at the most, it is preferable to 5nm��14nm.
Being not particularly limited, the aspect ratio of dull and stereotyped shape metallic particles suitably can be selected according to predetermined object, but from the higher angle of the reflectivity of particle in the infrared region of wavelength 800nm��wavelength 1800nm, aspect ratio is preferably 6��40, it is more preferable to be 10��35. When aspect ratio is less than 8, then reflecting wavelength and will be less than 800nm, and when aspect ratio is more than 40, then reflecting wavelength will be longer than 1800nm, thus this material can not ensure sufficient invisible heat reflection potential.
Aspect ratio refers to by by the calculated value of the median size (leveled circular equivalent diameter) of dull and stereotyped shape metallic particles divided by the average particle thickness of dull and stereotyped shape metallic particles. Average particle thickness is corresponding to the distance between two principal planes of dull and stereotyped shape metallic particles; Such as, as shown in Figure 4 A and 4 B shown in FIG., average particle thickness can use atomic force microscope (AFM) to measure.
Being not particularly limited, the method measuring average particle thickness with AFM suitably can be selected according to predetermined object. Such as, it can be mentioned following method, wherein, the particle dispersion comprising dull and stereotyped shape metallic particles is dripped on the glass substrate and drying thereon, then measure the thickness of a particle.
The domain of the existence of the dull and stereotyped shape metallic particles of 1-2-4.
In the heat ray shielding material of the present invention, the domain of the existence thickness of dull and stereotyped shape metallic particles is preferably 5nm��60nm, it is more preferable to is 11nm��60nm, is also more preferably 20nm��60nm.
Preferably, in the heat ray shielding material of the present invention, the hexagon of at least 80 number % to circular dull and stereotyped shape metallic particles is present in surface that metallic particles comprises layer in the scope of d/2, more preferably in the scope of d/3, it is even more preferred that, the hexagon of at least 60 number % to circular dull and stereotyped shape metallic particles exposes the surface that metallic particles comprises layer. The dull and stereotyped shape metallic particles existed to the scope of d/2 on the surface that metallic particles comprises layer refers to that at least part of dull and stereotyped shape metallic particles is included in surface that metallic particles comprises layer in the scope of d/2. In other words, part protrudes from the concept and range that the dull and stereotyped shape metallic particles on surface that metallic particles comprises layer is also in the dull and stereotyped shape metallic particles that the surface that metallic particles comprises layer exists to the scope of d/2 as shown in fig. 5e. Fig. 5 E refers to that each dull and stereotyped shape metallic particles only has part to be embedded in metallic particles in a thickness direction and comprises in layer, does not refer to that each dull and stereotyped shape metallic particles is layered on metallic particles and comprises on the surface of layer.
Expose the surperficial dull and stereotyped shape metallic particles that metallic particles comprises layer and refer to the surface that a surperficial part of dull and stereotyped shape metallic particles protrudes from metallic particles and comprises layer.
Herein, the existence distribution that dull and stereotyped shape metallic particles comprises in layer at metallic particles can be determined, such as observe, by the SEM of the section sample of heat ray shielding material, the image obtained, it may be determined that dull and stereotyped shape metallic particles comprises the distribution of the existence in layer at metallic particles.
In the heat ray shielding material of the present invention, desirably, metallic particles comprise layer 2 be present in apart from Fig. 5 B heat ray shielding material horizontal surface in the depth direction for (��/n)/4 scope in, wherein, the plasma resonance wavelength that metallic particles comprises the metal forming dull and stereotyped shape metallic particles 3 in layer is called ��, and the specific refractory power that metallic particles is comprised the medium in layer 2 is called n. Within the scope of this, comprising the phase place of the upper and lower interface of layer at the metallic particles of heat ray shielding material due to reflection wave, the reinforcing effect of echo amplitude will be enough high, and therefore the visible light transmissivity of this material and maximum heat x ray refractive index x will thus improve.
It is not particularly limited, the plasma resonance wavelength X comprising the metal forming dull and stereotyped shape metallic particles in layer at metallic particles suitably can be selected according to predetermined object, but from the angle that this layer is given invisible heat reflecting properties, wavelength is preferably 400nm��2500nm, from the angle that it gives visible light transmissivity, wavelength is more preferably 700nm��2500nm.
1-2-5. metallic particles comprises the medium in layer
Being not particularly limited, metallic particles comprises the medium in layer and suitably can select according to predetermined object. Preferably, in the heat ray shielding material of the present invention, metallic particles comprises layer and comprises polymkeric substance, it is more preferable to be transparency polymkeric substance. Polymkeric substance comprises various polymer substance, such as polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, plexiglass, polycarbonate resin, polyvinyl chloride (PVC) RESINS, (saturated) vibrin, urethane resin and natural polymer (such as gelatin and Mierocrystalline cellulose etc.). Wherein, in the present invention, it is desirable to, the principal polymeric of polymkeric substance is polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl chloride (PVC) RESINS, (saturated) vibrin or urethane resin. Dull and stereotyped shape metallic particles from the hexagon of at least 80 number % to circle can easily be present in surface that metallic particles comprises layer to the angle in the region of d/2, it is more preferable to be vibrin and urethane resin; From the angle of the rub resistance of the heat ray shielding material improving the present invention, it is even more preferred that vibrin.
In vibrin, from it, material is given the angle of excellent weathering resistance, it is even more preferred that not double bond containing saturated polyester resin. The angle of higher hardness, weather resistance and thermotolerance can be provided to provide with water-soluble/water-dispersible curing agent etc. from polymkeric substance, it is also preferred that, polymkeric substance has hydroxyl or carboxyl in its molecule end.
As polymkeric substance, it is preferred to use be commercially available polymkeric substance, such as, it can be mentioned the Polyester Resin Water Soluble PlascoatZ-867 that GooChemical manufactures.
In this manual, the principal polymeric that metal comprises the polymkeric substance comprised in layer refers to the polymeric constituent accounting for metal and comprising at least 50 quality % of polymkeric substance contained in layer.
Preferably, it is 1 quality %��10000 quality % that the content of vibrin comprises the metallic particles comprised in layer relative to metallic particles, also more preferably 20 quality %��500 quality %. When the content that metallic particles comprises the tackiness agent comprised in layer is limited in above-mentioned scope, then can improve the physical propertiess such as this layer such as rub resistance.
The specific refractory power n of medium is preferably 1.4��1.7.
Preferably, in the heat ray shielding material of the present invention, when the thickness of the dull and stereotyped shape metallic particles that hexagon is extremely circular is called a, the hexagon of at least 80 number % is coated with polymkeric substance to the scope of circular dull and stereotyped shape metallic particles at least a/10 in the thickness direction thereof, more preferably in the thickness direction thereof a/10��10a scope is coated with polymkeric substance, also more preferably in a/8��4a scope, it is coated with polymkeric substance. When the hexagon of at least predetermined proportion to circular dull and stereotyped shape metallic particles being embedded in metallic particles in the above described manner and comprises in layer, then the rub resistance of this layer will more improve further. Specifically, in the heat ray shielding material of the present invention, the enforcement mode of Fig. 5 D is more more preferred than the enforcement mode of Fig. 5 E.
The area ratio of the dull and stereotyped shape metallic particles of 1-2-6.
Area ratio [(B/A) �� 100] refers to, when from top view heat ray shielding material, the total area B of dull and stereotyped shape metallic particles relative to substrate area A (from vertical direction observe metallic particles comprise layer time, for metallic particles comprises the total projection area A of layer) ratio be preferably at least 15%, it is more preferable at least 20%. When area ratio is less than 15%, then the maximum heat x ray refractive index x of this material will reduce, and this material can not fully ensure its heat shielding effects.
The image of the image or AFM (atomic force microscope) observation acquisition that, such as the SEM by being carried out by the substrate of heat ray shielding material from top can observe acquisition herein carries out image procossing and determines area ratio.
The average grain spacing of the dull and stereotyped shape metallic particles of 1-2-7.
From the angle of the visible light transmissivity of this layer and maximum heat x ray refractive index x, metallic particles comprises at least 1/10 that the average grain spacing between dull and stereotyped shape metallic particles adjacent one another are in horizontal direction in layer is preferably the median size of dull and stereotyped shape metallic particles.
When dull and stereotyped shape metallic particles average grain spacing in the horizontal direction be less than dull and stereotyped shape metallic particles median size 1/10 time, the maximum heat x ray refractive index x of this layer reduces. From the angle of the visible light transmissivity of layer, the average grain spacing of horizontal direction is preferably random. When this distance is not random, that is, when this distance all for the moment, visible absorption can be there is and visible light transmissivity thus reduces.
Herein, dull and stereotyped shape metallic particles average grain spacing in the horizontal direction refers to the mean value of the grain spacing between two adjacent particle from data. Random average grain spacing refers to, " when by SEM image two value comprising at least 100 dull and stereotyped shape metallic particles to obtain the two-dimentional auto-correlation of brightness value, then result does not have any other significance maximal point beyond initial point ".
1-2-8. metallic particles comprises the layer structure of layer
In the heat ray shielding material of the present invention, as shown in Fig. 5 A��Fig. 5 E, dull and stereotyped shape metallic particles comprises the form configuration of layer with the metallic particles comprising dull and stereotyped shape metallic particles.
Metallic particles comprises layer and can be made up of the such as individual layer shown in Fig. 5 A��Fig. 5 E, or can also comprise layer by multiple metallic particles and form. When metallic particles comprise layer be made up of multiple layer, it is possible to according to the wavelength region that will give thermal shielding capability, this layer given any required thermal shielding capability. When metallic particles comprise layer be made up of multiple layer, required is, at least outer metallic particles at the heat ray shielding material of the present invention comprises in layer, the hexagon of at least 80 number % to circular dull and stereotyped shape metallic particles is present in surface that outer metallic particles comprises layer to, in the scope of d'/2, wherein d' represents that outer metallic particles comprises the thickness of layer.
1-2-9. metallic particles comprises the thickness of layer
In the heat ray shielding material of the present invention, the thickness that metallic particles comprises layer is 10nm��80nm. It is preferred that the thickness that metallic particles comprises layer is 20nm��80nm, also more preferably 30nm��50nm. The thickness d that metallic particles comprises layer is preferably a��10a, it is more preferable to is 2a��8a, is also more preferably 1a��5a, and wherein, a represents the thickness of hexagon to circular dull and stereotyped shape metallic particles.
Herein, the thickness that each metallic particles comprises layer can such as be determined on the image obtained by the SEM observation of the section sample of heat ray shielding material.
When the metallic particles of heat ray shielding material comprise layer is configured with such as following top coating etc. any other layer, other layers described comprise the border between layer and can determine in the way of identical with aforesaid way with metallic particles, and the thickness d that metallic particles comprises layer can also be determined in the way of identical with aforesaid way. When use comprise coated film that the identical polymkeric substance formation metallic particles of the polymer type comprised in layer comprises on layer with metallic particles, usually, metallic particles comprises the border between layer and coated film and can determine on the image that SEM observes acquisition, and the thickness d that metallic particles comprises layer can thus be determined.
The synthetic method of the dull and stereotyped shape metallic particles of 1-2-10.
Being not particularly limited, the synthetic method of dull and stereotyped shape metallic particles suitably can be selected according to predetermined object, as long as can synthesize hexagon in this synthetic method to circular dull and stereotyped shape metallic particles. Such as, it can be mentioned liquid phase method, such as chemical reduction method, photoreduction method or electrochemical reducing etc. In these methods, from the angle of shape and size control property, it is particularly preferred to such as liquid phase methods such as chemical reduction method or photoreduction methods. Synthesis hexagon to trilateral dull and stereotyped shape metallic particles after, this particle can use the dissolved species (such as nitric acid or Sodium Nitrite etc.) that can dissolve silver to etch, then undertaken aging by heating etc., thus make hexagon to the obtuse angle, angle of the dull and stereotyped shape metallic particles of trilateral, thus obtain predetermined hexagon to circular dull and stereotyped shape metallic particles.
About other synthetic method any of dull and stereotyped shape metallic particles in addition to the method described above, crystal seed can be fixed on the surface of transparency carrier (such as film or glass), then can grow flat plate-shape metal (such as Ag) particle by lenticular thereon.
In the heat ray shielding material of the present invention, it is possible to dull and stereotyped shape metallic particles is processed further, to give required character. Being not particularly limited, extra process suitably can be selected according to predetermined object. Such as, it can be mentioned form high refractive index shell and add additive as various in dispersion agent and antioxidant etc.
1-2-10-1. the formation of high refractive index shell
In order to improve visible transparent further, dull and stereotyped shape metallic particles can be coated with the higher high-index material of visible transparent.
Being not particularly limited, high-index material suitably can be selected according to object. Such as, it can be mentioned TiOx��BaTiO3��ZnO��SnO2��ZrO2��NbOxDeng.
Being not particularly limited, coating method suitably can be selected according to predetermined object. Such as, can be used on the surface of silver-colored dull and stereotyped shape metallic particles herein to be hydrolyzed four titanium butoxide form TiOxThe method of layer, such as Langmuir, the 2000,16th volume, the report of 2731st��2735 pages.
When being difficult to direct formation high refractive index metal oxide shell on dull and stereotyped shape metallic particles, other method can be used herein, wherein, after synthesizing dull and stereotyped shape metallic particles in the manner, suitably form SiO subsequently thereon2Or the shell of polymkeric substance, and on shell, form above-mentioned metal oxide layer further.At use TiOxAs in the situation of the material of high refractive index metal oxide layer, there is photocatalytic activity TiOxThe matrix deterioration being wherein dispersed with dull and stereotyped shape metallic particles may be made, therefore, in this case, dull and stereotyped shape metallic particles forms TiOxLayer after, it is possible to according to predetermined object optional form SiO2Layer.
1-2-10-2. the interpolation of various additive
Metallic particles in the heat ray shielding material of the present invention comprises the principal polymeric that layer comprises polymkeric substance and this polymkeric substance when being vibrin, from the angle of film toughness, it is necessary to add linking agent in this material. Linking agent is not particularly limited, it can be mentioned epoxy type, isocyanate-based, melamine-type, carbodiimide type, azoles quinoline type and other linking agents. Wherein, it is preferred that carbodiimide type and azoles quinoline type linking agent. The specific examples of carbodiimide type linking agent comprises: such as CarbodiliteV-02-L2 (NisshinBoseki manufacture) etc. Preferably, the amount of the component coming from linking agent that this material comprises comprises 1 quality %��20 quality % of total binder in layer for metallic particles, it is more preferable to be 2 quality %��20 quality %.
Metallic particles in the heat ray shielding material of the present invention comprises layer when comprising polymkeric substance, from preventing the angle shunk to form the good layer of surface topography, it is desirable to add tensio-active agent in this material. As tensio-active agent, any known tensio-active agent can be used herein, such as anionic and nonionic surface active agent etc. The specific examples of tensio-active agent used herein comprises, such as, and LupizolA-90 (NOF manufacture) and NaroactyHN-100 (SanyoChemical manufacture) etc. Preferably, tensio-active agent comprises 0.05 quality %��10 quality % of whole tackiness agent in layer containing promising metallic particles, it is more preferable to be 0.1 quality %��5 quality %.
In order to prevent the metal (such as silver) forming dull and stereotyped shape metallic particles to be oxidized, dull and stereotyped shape metallic particles can have absorption antioxidant thereon, such as mercapto-tetrazole or xitix etc. In addition, or in order to anti-oxidation, it is possible to form the oxidation sacrifice layer of Ni etc. on the surface of dull and stereotyped shape metallic particles. In order to make it shield oxygen, particle can be coated with SiO2Deng metal oxide film.
Such as, in order to give dispersibility to dull and stereotyped shape metallic particles, it is possible to add in dull and stereotyped shape metallic particles and comprise in N element, S element and P element at least any one lower molecular weight dispersion agent and high molecular weight dispersant etc., such as quaternary ammonium salt or amine etc.
2. other layers
2.1 bonding coat
Preferably, the heat ray shielding material of the present invention has bonding coat. Bonding coat can comprise UV light absorber.
Being not particularly limited, the material that can be used for being formed bonding coat suitably can be selected according to predetermined object; Such as, it can be mentioned polyvinyl butyral acetal (PVB) resin, acrylic resin, styrene/acrylic system resin, carbamate resins, vibrin and silicone resin etc. One or more of these resins may be used singly or in combin at this. The bonding coat comprising these materials can be formed by coating.
In addition, such as static inhibitor, lubricant or anti blocking agent etc. can be added in bonding coat.
Preferably, the thickness of bonding coat is 0.1 ��m��10 ��m.
2.2 substrate
Preferably, the heat ray shielding material of the present invention has substrate with the hexagon with at least 80 number % located in off-centered mode to the side that the face side of circular dull and stereotyped shape metallic particles is contrary what metallic particles comprised layer.
Being not particularly limited, substrate can be any light-transmitting substrate, it is possible to suitably select according to predetermined object. Such as, it can be mentioned this visible light transmissivity is the substrate of more than 70% or preferably more than 80%, and there is the substrate of high near infrared ray transmitance.
The shape of substrate, structure, size and material etc. are not particularly limited, it is possible to suitably select according to predetermined object. Shape can be dull and stereotyped shape etc.; Structure can be single layer structure or rhythmo structure; And size suitably can select according to the size of heat ray shielding material.
Being not particularly limited, baseplate material suitably can be selected according to predetermined object. Such as, it can be mentioned the film that following material is formed: polyolefin resin, such as polyethylene, polypropylene, poly(4-methyl-1-pentene) and poly 1-butene etc.; Vibrin, such as polyethylene terephthalate and Polyethylene Naphthalate etc.; Polycarbonate resin; Polyvinyl chloride (PVC) RESINS; Polyphenylene sulfide; Polyethersulfone resin; Poly-ethyl-sulfide resin; Polyphenylene oxide resin; Styrene resin; Acrylic resin; Polyamide resin; Polyimide resin; And celluosic resin (such as rhodia) etc., and by the stacked film of these resin formation. In these films, it is especially preferred that polyethylene terephthalate film.
Being not particularly limited, the thickness of substrate film suitably can be selected according to the intended purpose of solar energy shielding film. Usually, this thickness can be about 10 ��m��about 500 ��m, it is preferable to 12 ��m��300 ��m, it is more preferable to is 16 ��m��125 ��m.
2-3. hard coat
In order to give rub resistance to it, it is preferred that functional membrane has hard coat, and described hard coat has hard coating function. Hard coat can comprise metal oxide particle.
Being not particularly limited, hard coat suitably can be selected in the forming method of its type and this layer according to predetermined object. Such as, it can be mentioned heat embrittlement or heat reactive resin, such as acrylic resin, silicone resin, melamine resin, carbamate resins, Synolac and fluoro-resin etc. Being not particularly limited, the thickness of hard coat suitably can be selected according to predetermined object. Preferably, this thickness is 1 ��m��50 ��m. On hard coat, preferably form anti-reflecting layer and/or anti-dazzle layer further, thus can obtain the functional membrane also except there is rub resistance with anti-reflective and/or anti-glare properties. Hard coat can comprise above-mentioned metal oxide particle.
2-4. pushes up coating
In order to the oxidation/sulfuration preventing its middle plateform shape metallic particles from causing because of mass transfer, and in order to give scratch resistance to this material, the heat ray shielding material of the present invention can have top coating, and the hexagon that exposes that this top coating comprises layer with metallic particles directly contacts to the surperficial of circular dull and stereotyped shape metallic particles. This material can have the top coating comprising between layer and following UV-absorbing layer at metallic particles. Particularly, the metallic particles being arranged in the heat ray shielding material of the present invention at dull and stereotyped shape metallic particles in off-centered mode comprises the surface of layer, in order to prevent dull and stereotyped shape metallic particles from peeling off in production stage and pollute, and in order to prevent the structure of dull and stereotyped shape metallic particles chaotic when metallic particles comprises and forms other any layer on layer, this material can have this kind of top coating.
Top coating can comprise UV light absorber.
Being not particularly limited, top coating suitably can be selected according to predetermined object.Such as, this layer comprises tackiness agent, matting agent and tensio-active agent, it is possible to selection of land can comprise any other composition.
Being not particularly limited, tackiness agent suitably can be selected according to predetermined object. Such as, it can be mentioned thermosetting resin or heat-curing resin, such as acrylic resin, silicone resin, melamine resin, carbamate resins, Synolac, fluoro-resin etc.
The thickness of top coating is preferably 0.01 ��m��1000 ��m, it is more preferable to is 0.02 ��m��500 ��m, is also more preferably 0.1 ��m��10 ��m, is still more preferably 0.2 ��m��5 ��m.
2-5. UV light absorber
Preferably, the heat ray shielding material of the present invention has the layer comprising UV light absorber.
Such as, the layer comprising UV light absorber suitably can be selected according to predetermined object, it is possible to is bonding coat, or is in bonding coat and layer (pushing up coating etc.) that metallic particles comprises between layer. In any situation, it is desirable to, add to UV light absorber to be arranged on and comprise layer relative to metallic particles and be exposed in the layer of the side of daylight.
Being not particularly limited, UV light absorber suitably can be selected according to predetermined object. Such as, it can be mentioned benzophenone class UV light absorber, benzotriazole category UV light absorber, triazine-based ultraviolet absorption agent, salicylate ultraviolet absorption agent and cyanoacrylate ultraviolet absorption agent etc. Can be used alone a kind of of these UV light absorber herein or combinationally use wherein two or more dissimilar.
Being not particularly limited, benzophenone class UV light absorber suitably can be selected according to predetermined object. Such as, it can be mentioned 2,4-hydroxyl-4-methoxyl group-5-sulfo group benzophenone etc.
Being not particularly limited, benzotriazole category UV light absorber suitably can be selected according to predetermined object. Such as, 2-(5-chloro-2H-benzotriazole-2-base)-4-methyl-6-tert butyl phenol (Tinuvin326), 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole and 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-5-chlorine benzotriazole etc. can be mentioned.
Being not particularly limited, triazine-based ultraviolet absorption agent suitably can be selected according to predetermined object. Such as, it can be mentioned single (hydroxy phenyl) triaizine compounds, two (hydroxy phenyl) triaizine compounds and three (hydroxy phenyl) triaizine compounds etc.
Such as, single (hydroxy phenyl) triaizine compounds comprises 2-[4-[(2-hydroxyl-3-dodecane oxygen base propyl group) oxygen base]-2-hydroxy phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[4-[(2-hydroxyl-3-tridecane oxygen base propyl group) oxygen base]-2-hydroxy phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2, 4-dihydroxy phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(the different octyloxyphenyl of 2-hydroxyl-4-)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine and 2-(2-hydroxyl-4-dodecane oxygen base phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine etc. such as, two (hydroxy phenyl) triaizine compounds comprises 2, two (2-hydroxyl-4-propoxy-the phenyl)-6-(2 of 4-, 4-3,5-dimethylphenyl)-1,3, two (2-hydroxy-3-methyl-4-propoxy-the phenyl)-6-(4-aminomethyl phenyl)-1,3 of 5-triazine, 2,4-, 5-triazine, 2, two (2-hydroxy-3-methyl-4-hexyloxy the phenyl)-6-(2,4-3,5-dimethylphenyl)-1,3 of 4-, 5-triazine and 2-phenyl-4, two [2-hydroxyl-4-[3-(methoxyl group seven oxyethyl group)-2-hydroxy propyloxy group] phenyl]-1,3,5-triazines of 6-etc.Such as, three (hydroxy phenyl) triaizine compounds comprises 2, two (2-hydroxyl-4-the butoxy phenyl)-6-(2 of 4-, 4-dibutoxy phenyl)-1, 3, 5-triazine, 2, 4, 6-tri-(2-hydroxyl-4-octyloxyphenyl)-1, 3, 5-triazine, 2, 4, 6-tri-[2-hydroxyl-4-(3-butoxy-2-hydroxy propyloxy group) phenyl]-1, 3, 5-triazine, 2, two [2-hydroxyl-4-[1-(different carbonyl octyloxy) oxyethyl group] the phenyl]-6-(2 of 4-, 4-dihydroxy phenyl)-1, 3, 5-triazine, 2, 4, 6-tri-[2-hydroxyl-4-[1-(different carbonyl octyloxy) oxyethyl group] phenyl]-1, 3, 5-triazine and 2, two [2-hydroxyl-4-[1-(different carbonyl octyloxy) oxyethyl group] the phenyl]-6-[2 of 4-, two [1-(different carbonyl octyloxy) oxyethyl group] phenyl of 4-]-6-[2, two [1-(different carbonyl octyloxy) oxyethyl group] phenyl of 4-]-1, 3, 5-triazine etc.
Being not particularly limited, salicylate ultraviolet absorption agent suitably can be selected according to predetermined object. Such as, it can be mentioned phenyl salicylate, Whitfield's ointment to tert-butyl-phenyl ester, Whitfield's ointment to octyl phenyl ester and Neo Heliopan OS etc.
Being not particularly limited, cyanoacrylate ultraviolet absorption agent suitably can be selected according to predetermined object. Such as, it can be mentioned 2-ethylhexyl-2-cyano group-3,3-diphenylacrylate ester and ethyl-2-cyano group-3,3-diphenylacrylate ester etc.
Being not particularly limited, tackiness agent suitably can be selected according to predetermined object, and but, tackiness agent preferably has higher visible transparent and the tackiness agent of the sun power transparency. Such as, it can be mentioned acrylic resin, polyvinyl butyral acetal and polyvinyl alcohol etc. When tackiness agent absorbs invisible heat, the reflecting effect of dull and stereotyped shape metallic particles can thus weaken, therefore for the UV-absorbing layer formed between invisible heat source and dull and stereotyped shape metallic particles, desirably select the material in 450nm��1500nm region without absorption, and reduce the thickness of UV-absorbing layer.
The thickness of UV-absorbing layer is preferably 0.01 ��m��1000 ��m, it is more preferable to be 0.02 ��m��500 ��m. When thickness is less than 0.01 ��m, then ultraviolet radiation absorption will be not good; And when thickness is more than 1000 ��m, then visible light transmissivity may reduce.
The content of UV-absorbing layer is different according to the UV-absorbing layer used, thus can not indiscriminate regulation. Preferably, suitably select this content, the ultraviolet ray transmissivity needed for giving with the heat ray shielding material to the present invention.
Ultraviolet ray transmissivity is preferably at the most 5%, it is more preferable to be at the most 2%. When ultraviolet ray transmissivity is more than 5%, the color that dull and stereotyped shape metallic particles comprises layer changes due to the ultraviolet in daylight.
2-6. metal oxide particle
In order to absorb long-wave infrared, and from the angle of heat ray shielding ability and the balance of its production cost, the heat ray shielding material of the present invention selection of land can comprise at least one metal oxide particle. in this case, such as, it is desirable to, hard coat 5 comprises metallic particles. hard coat 5 can be layered in metallic particles through substrate 1 and comprise on layer 2. when the configuration of the heat ray shielding material of the present invention make metallic particles comprise layer 2 can be positioned at the side received such as invisible heats such as sunlights, metallic particles comprises layer 2 can the invisible heat that it applied of reflecting part (or can selection of land whole), and hard coat 5 can absorption portion invisible heat, result, the summation of following heat can be reduced: owing to not comprising the heat absorbing in layer and entering the heat ray shielding material that the invisible heat of heat ray shielding material causes and directly accept from inside at metal oxide, with by the metal oxide particle of heat ray shielding material comprise layer absorb and indirect transfer to the heat of the inside of heat ray shielding material.
Being not particularly limited, the material of metal oxide particle suitably can be selected according to predetermined object. Such as, it can be mentioned the Indium sesquioxide (being hereinafter abbreviated as " ITO ") of mixing tin, weisspiessglanz (being hereinafter abbreviated as " ATO "), zinc oxide, titanium oxide, Indium sesquioxide, stannic oxide, weisspiessglanz and the glass-ceramic etc. mixing tin. Wherein, it is more preferable to be ITO, ATO and zinc oxide, this is because it has excellent invisible heat receptivity and can manufacture the heat ray shielding material with wide region invisible heat receptivity when combining with dull and stereotyped shape Argent grain. Particularly preferably be ITO because its can stop the wavelength of at least 90% be the infrared rays of more than 1200nm and have at least 90% visible light transmissivity.
Preferably, in order to not make the visible light transmissivity of particle reduce, the volume average particle size of a particle of metal oxide particle is 0.1 ��m at the most.
Being not particularly limited, the shape of metal oxide particle suitably can be selected according to predetermined object. Such as, this particle can be spherical, needle-like, tabular or analogous shape.
Being not particularly limited, the content that metal oxide particle comprises the metal oxide particle in layer suitably can be selected according to predetermined object. Such as, this content is preferably 0.1g/m2��20g/m2, it is more preferable to it is 0.5g/m2��10g/m2, also it is more preferably 1.0g/m2��4.0g/m2��
When content is less than 0.1g/m2Time, then the amount at sunshine that skin can be felt may increase, and when content is more than 20g/m2Time, the visible light transmissivity of this layer may be deteriorated. On the other hand, when content is 1.0g/m2��4.0g/m2Shi Yinwei can avoid aforementioned two problems and favourable.
Such as, the content that metal oxide particle comprises the metal oxide particle in layer can be determined as follows: observes the ultrathin section(ing) TEM image of heat ray shielding layer and the SEM image on its surface, measures number and its median size of the metal oxide particle in given area; By the quality (g) obtained based on the particle number of metal oxide particle, median size and proportion divided by given area (m2) thus obtain content. In another way, the metal oxide particle of given area is comprised the metal oxide microparticle stripping in layer in methyl alcohol, the quality (g) of metal oxide particle is recorded by fluorescent X-ray, and by this quality divided by given area (m2) to obtain content.
3. the manufacture method of heat ray shielding material
Being not particularly limited, the manufacture method of the heat ray shielding material of the present invention suitably can be selected according to predetermined object. Such as, it can be mentioned on the surface of aforesaid substrate, form the coating method that above-mentioned metallic particles comprises layer, above-mentioned UV-absorbing layer and optional other layers.
3-1. metallic particles comprises the forming method of layer
Being not particularly limited, the forming method that the metallic particles of the present invention comprises layer suitably can be selected according to predetermined object. Such as, it can be mentioned following method: be coated with, with the use of dip coater, mould, the method that machine, slit type coater, metering bar coater or intaglio plate coating machine etc. carry out being coated with and apply the dispersion liquid comprising above-mentioned dull and stereotyped shape metallic particles on the surface of the bottom layers such as such as aforesaid substrate; And the method for planar orientation is carried out according to LB embrane method, self-assembly method or spraying method etc. When manufacturing the heat ray shielding material of the present invention, first prepare the composition that the metallic particles shown in the embodiment hereafter provided comprises layer, add latex etc. wherein so that above-mentioned hexagon to the circular dull and stereotyped shape metallic particles of at least 80 number % can be present in surface that metallic particles comprises layer in the scope of its d/2.Preferably, the above-mentioned hexagon of at least 80 number % to circular dull and stereotyped shape metallic particles is present in surface that metallic particles comprises layer in the scope of its d/3. The addition of latex is not particularly limited. Such as, latex preferably adds with the amount of 1 quality %��10000 quality % of dull and stereotyped shape metallic particles.
If desired, after coating, it is possible to the use of the planar orientation such as rolling the backer roll such as roller or laminating roll and promoting dull and stereotyped shape metallic particles.
3-2. pushes up the forming method of coating
Preferably, push up coating to be formed by coating. Coating process is not particularly limited, it is possible to use any currently known methods. Such as, it can be mentioned use dip coater, mould painting machine, slit type coater, metering bar coater or intaglio plate coating machine etc. to be coated with the method for the dispersion liquid comprising above-mentioned UV light absorber.
The forming method of 3-3. hard coat
Preferably, hard coat is formed by coating. Coating process is not particularly limited, it is possible to use any currently known methods. Such as, it can be mentioned use dip coater, mould painting machine, slit type coater, metering bar coater or intaglio plate coating machine etc. to be coated with the method for the dispersion liquid comprising above-mentioned UV light absorber.
The forming method of 3-4. bonding coat
Preferably, bonding coat is formed by coating. Such as, bonding coat can be layered on the surface of bottom layer, and bottom layer such as aforesaid substrate, above-mentioned metallic particles comprise layer and above-mentioned UV-absorbing layer etc. Coating process is not particularly limited, it is possible to use any currently known methods.
4. the characteristic of the heat ray shielding material of the present invention
Preferably, the maximum value of the solar reflectance of the heat ray shielding material of the present invention appears at (preferred 800nm��1,800nm) within the scope of 600nm��2,000nm, to increase the invisible heat reflectivity of this material. In practice, it is necessary to maximum heat x ray refractive index x is at least 30%, it is preferable at least 50%; Visible light transmissivity is needed to be at least 70%, it is more preferable to at least 75%.
Preferably, the visible light transmissivity of the heat ray shielding material of the present invention is at least 60%, it is more preferable to at least 70%. When visible light transmissivity is less than 60%, then this material for when vehicle glass or buildings glass observe exterior object there will be problem.
Preferably, the ultraviolet ray transmissivity of the heat ray shielding material of the present invention is at the most 5%, it is more preferable to be at the most 2%. When ultraviolet ray transmissivity is greater than 5%, then the ultraviolet because of daylight is changed by the color that dull and stereotyped shape metallic particles comprises layer.
Preferably, the mist degree of the heat ray shielding material of the present invention is at the most 20%. When mist degree is greater than 20%, then owing to this material is there will be problem for observing exterior object when vehicle glass or buildings glass, and it is unfavorable for security.
The using forestland of heat ray shielding material and laminate structure
Use the dry type stacking of bonding coat
Heat ray shielding material film in the present invention is used for giving in functional situation to existing pane etc., and this film can adhere to the indoor of pane via tackiness agent by stacking thereon. In this kind of situation, owing to being possible to prevent heat generation, it is desirable to, make reflecting layer as much as possible towards daylight side, therefore, it is suitable that, bonding coat is layered in Nano silver piece particle comprise on layer, and this material is adhered on pane via bonding coat.
When bonding coat is laminated on silver nanoparticle lamella, tackiness agent can be contained the direct paint of liquid its on the surface; But, the various additive comprised in bonding coat and the fluidizer of employing and solvent may upset the arrangement of silver nanoparticle lamella, or Nano silver piece self is deteriorated. In order to make this kind of puzzlement minimized, effectively, using following dry type stacking: wherein, in advance by adhesive application to antiadhesion barrier and thereon dry to prepare bonding film, and the silver nanoparticle lamella that the adhesive surface of gained film is laminated to the film of the present invention is on the surface.
Laminate structure
By by the heat ray shielding material of the present invention and any glass or plastic lamination, it is possible to obtained laminate structure.
Being not particularly limited, manufacture method suitably can be selected according to predetermined object. Can mention, by heat ray shielding material adhesion obtained in the above described manner on the vehicle glass such as such as automobile or plastics or buildings glass or plastics.
The heat ray shielding material of the present invention may be used for selective reflection or the absorption of the invisible heat (near infrared ray) of any pattern; Being not particularly limited, the using forestland of this material suitably can be selected according to predetermined object. Such as, it can be mentioned, the film etc. of vehicle film or laminate structure, buildings film or laminate structure and agricultural use. Wherein, from the angle of energy-saving effect, it is preferred that vehicle film or laminate structure and buildings film or laminate structure.
In the present invention, invisible heat (near infrared ray) refers to the near infrared ray (780nm��1800nm) comprised in daylight with the ratio of about 50%.
Embodiment
The characteristic of the present invention is more specifically described with reference to the embodiment hereafter provided.
In the following embodiments, the material, consumption, ratio, process details and the treating processes that use can suitably change or change, as long as not deviateing the scope of the present invention. Therefore, the scope of the present invention should not be interpreted as to being limited property the embodiment of following offer.
Comparative example 1
The synthesis of dull and stereotyped shape metallic particles
To, in the 2.5mM sodium citrate aqueous solution of 50mL, adding the 0.5g/L polystyrolsulfon acid aqueous solution of 2.5mL and be heated to 35 DEG C. To, in above-mentioned solution, adding the 10mM sodium borohydride aqueous solution of 3mL, under stirring, add the 0.5mM silver nitrate aqueous solution of 50mL with the speed of 20mL/ minute. By gained solution stirring 30 minutes thus obtained grain kind solution.
In the reactor, the ion exchanged water of 87.1mL is added in the 2.5mM sodium citrate aqueous solution of 132.7mL, it is heated to 35 DEG C. The solution of reactor adds the 10mM aqueous ascorbic acid of 2mL, adds the grain kind solution of 21.1mL wherein, under stirring, add the 0.5mM silver nitrate aqueous solution of 79.6mL wherein with the speed of 10mL/ minute. Hereafter stir 30 minutes, in reactor, add the 0.35M hydroquinone sulfonic acid aqueous solutions of potassium of 71.1mL, and in reactor, add the 7 quality % aqueous gelatin solutions of 200g. By mixing the 0.47M silver nitrate aqueous solution of the 0.25M sodium sulfite solution of 107mL and 107mL and obtained white precipitate mixed solution adds in the solution of reactor. After adding white precipitate mixed solution, in reactor, at once add the 0.83MNaOH aqueous solution of 72mL. In this stage, the interpolation speed of the NaOH aqueous solution is controlled, so that the pH of system can not more than 10. It is stirred 300 minutes to obtain the dispersion liquid of dull and stereotyped shape Argent grain.
According to following method, the characteristic of the metallic particles in the dull and stereotyped shape Argent grain dispersion liquid thus obtained is evaluated. Through confirming, in dull and stereotyped shape Argent grain dispersion liquid, define the hexagonal flat plate-like particles (being hereafter called hexagonal dull and stereotyped shape Argent grain) that leveled circular equivalent diameter is the silver of 300nm. The thickness of this hexagonal flat plate-like particles is through being measured as average 19nm. Known define the flat plate-like particles that aspect ratio is 15.8.
The evaluation of metallic particles
(ratio of flat plate-like particles, median size (leveled circular equivalent diameter) and coefficient of variation)
The shape homogeneity of dull and stereotyped shape Ag particle is determined as follows: the shape analyzing 200 particles of random sampling on the SEM image observed.In these particles, hexagon is called A to circular dull and stereotyped shape metallic particles, the irregular particles such as such as teardrop shaped or the particle that is less than other Polygons particles hexagonal are called B; The ratio (number %) of particle A is gone out by image analysis calculation. Gained result is as shown in table 1 below.
Similarly, 100 particle A particle diameter separately is measured with digital display calliper, and this data fetch is on average obtained mean value, it is as the median size (leveled circular equivalent diameter) of flat plate-like particles A, by the standard deviation of size distribution obtains the coefficient of variation (%) of the leveled circular equivalent diameter (size distribution) of flat plate-like particles A divided by median size (leveled circular equivalent diameter). Gained result is as shown in table 1 below.
Average particle thickness
Dispersant liquid drop containing the dull and stereotyped shape metallic particles formed to some extent is on the glass substrate and thereon dry, the thickness of a dull and stereotyped shape metallic particles A is measured by atomic force microscope (AFM) (NanocuteII, SeikoInstrumentsInc. manufacture). Using the measuring condition of AFM as follows: to use Autonomous test type sensor, adopt DFM pattern, useful range is 5 ��m, and scanning speed is 180 seconds/1 frame, and fractional data is 256 �� 256. The mean value of gained data is the average particle thickness of flat plate-like particles A. Gained result is as shown in table 1.
In addition, from the median size (leveled circular equivalent diameter) of thus obtained dull and stereotyped shape metallic particles A and average particle thickness, it is possible to by median size (leveled circular equivalent diameter) to be obtained the aspect ratio of flat plate-like particles A divided by average particle thickness.
Metallic particles comprises the formation of layer
The dull and stereotyped shape Argent grain dispersion liquid of 500mL in separating centrifuge (H-200N of Kokusan, AmbleRotorBN manufacture) with centrifugal 30 minutes of 7,000rpm so that hexagonal dull and stereotyped shape Argent grain precipitates out. After centrifugal, remove the supernatant liquor of 450mL, 200mL pure water is added in resistates, with the hexagonal dull and stereotyped shape Argent grain redispersion that will precipitate, thus obtained dull and stereotyped shape silver dispersion liquid.
In addition, following compound is added to prepare coating fluid.
[changing 1]
Compound 1
No. 14 line is used to be coated with rod (R.D.S.WebsterN.Y. manufacture), by coating fluid in PET film (CosmoshineA4300, Toyobo manufacture, thickness: 75 ��m), drying, to generate the film being fixed with hexagonal dull and stereotyped shape Argent grain on it.
By the heat ray shielding material of the obtained comparative example 1 of said process.
(thickness of flat plate-like particles domain of the existence)
In the heat ray shielding material of thus obtained comparative example 1, measure the thickness of flat plate-like particles domain of the existence according to following method. Gained result is as shown in table 1 below.
Sample through coating is being imbedded in epoxy resin, it may also be useful to it is cut by micro-slicing machine, and to obtain ultrathin section(ing), this section uses the S-5500 type FE-SEM of HitachiTechnologies to carry out STEM observation subsequently.
(total thickness of coating)
In the heat ray shielding material of the comparative example 1 of gained, the total thickness of above-mentioned coating is determined as follows (dry metallic particles comprises the mean thickness of layer): use laser microscope (VK-8510, Keyence manufactures), measure the thickness of the PET film without coating solution, and the thickness of the PET film after coating solution, heating, dry solidification. Calculate the thickness of uncoated film and the difference between the thickness of coated film. To the data fetch of 10 points in a sample on average to obtain the total thickness of coating. Gained result is as shown in table 1 below.
Comparative example 2��4
Change the amount of PlascoatZ687 in the coating fluid of comparative example 1, to prepare the heat ray shielding material sample of the comparative example 2��4 shown in following table 1.
Comparative example 5 and embodiment 1��3
Prepare the heat ray shielding material sample of comparative example 5 and embodiment 1��3 in the way of similar to comparative example 1, difference is, the addition of the grain kind solution in comparative example 1 is changed into 53mL, after adding white precipitate mixed solution, in reactor, add the 0.12MNaOH aqueous solution of 72mL but not the 0.83MNaOH aqueous solution of 72mL, and change the addition of PlascoatZ687 so that the thickness of coating can be as shown in table 1.
Comparative example 6 and embodiment 4��7
Prepare the heat ray shielding material sample of comparative example 6 and embodiment 4��7 in the way of similar to comparative example 1, difference is, do not add 2.5mM sodium citrate aqueous solution and the ion exchanged water of 132.7mL, the addition that grain is planted solution changes into 350mL, after adding white precipitate mixed solution, in reactor, do not add the 0.83MNaOH aqueous solution of 72mL, and change the addition of PlascoatZ687 so that the thickness of coating can be as shown in table 1.
Evaluate
The evaluation of optical property (maximum heat x ray refractive index x and visible light transmissivity)
Maximum heat x ray refractive index x is determined as follows: measures according to JIS-R3106:1998 " testing method (TestMethodforTransmittance; Reflectance; Emittance; SolarAcquisitionRate) of transmitance, reflectivity, emittance and solar energy acquisition rate " and calculates the invisible heat reflectivity of each sample, and the maximum value (being corrected by the spectral intensity of the direct solar radiation of each wavelength) within the scope of 300nm��2100nm is called maximum heat x ray refractive index x.
The visible light transmissivity at each wavelength place recorded in 380nm��780nm wavelength region by the spectrum luminous intensity factor correction at this wavelength place by the visible light transmissivity of analysis sample. Gained result is as shown in table 1 below.
The evaluation of surface topography
On a surface of the heat ray shielding material obtained at embodiment and comparative example, the point defect number that size (diameter) is more than 0.1mm is counted, to provide the numerical value of every square metre, as the index of surface topography. Gained result is as shown in table 1 below.
Every square metre of number of the point defect that size (diameter) is more than 0.1mm needs in practice for 2.0 point defect/m at the most2, it is more preferable to it is 1 point defect/m at the most2��
The evaluation of rub resistance
By 1cm2Hard plate be fixed in the friction tips of friction testing meter. The vessel of surface smoothing are clamped in embodiment and comparative example top and the bottom of the heat ray shielding material obtained. At room temperature 25 DEG C, apply the load of 300g to hard plate, and use friction tips rubbed sample, change friction frequency simultaneously in testing. Friction condition is as follows:
Frictional distance (one way): 5cm
Friction velocity the: come and go/second about 0.5 time
After friction, observe sample. The friction frequency that the rub resistance of sample peels off by causing film as follows is evaluated:
D: film peels off in 0��3 double rubs;
C: film peels off in 3��10 double rubs;
B: film peels off in 10��30 double rubs;
A: film does not peel off after 30 double rubs yet.
Gained result is as shown in table 1 below.
As shown in Table 1, when finding that use leveled circular equivalent diameter is the ultra-thin panel shape Argent grain of 14nm at the most in the present invention, and when being formed the metallic particles falling into limited range of the present invention by coating and comprise thin layer, then this material can meet good optical characteristics and good surface topography, can have the rub resistance of improvement simultaneously. Although the mechanism making dull and stereotyped shape metallic particles be located in surface in off-centered mode is not yet fully illustrated, but, it is believed that important, metallic particles be coated with and dry time must necessary float on fluid surface, and need to keep the surface tension that may change when drying to balance.
On the other hand, from comparative example 1��4 it will be seen that when the average particle thickness of flat plate-like particles is greater than the upper limit that the present invention limits, even if reducing the total coating thickness that metallic particles comprises layer, surface topography can also improve gradually;But, surface topography reach put into practice acceptable level time, then rub resistance be deteriorated, that is, surface topography and rub resistance can not be met in this case simultaneously. From comparative example 5 and 6 it will be seen that when the total thickness of coating is greater than the upper limit that the present invention limits, even if then reducing the average particle thickness of flat plate-like particles, surface topography is also deteriorated, that is, can not meet surface topography and rub resistance in this case simultaneously.
On the other hand, the heat ray shielding material obtained in embodiment and comparative example all buries in the epoxy, and uses cooled with liquid nitrogen. Use blade that it is carried out vertical direction cutting, to prepare the vertical cross-sectional sample of this material. Use the vertical cross-sectional sample of sem observation, and observe in the visual field pitch angle between 100 dull and stereotyped shape metallic particles and the horizontal plane of substrate (corresponding to Fig. 5 A �� ��). Gained data fetch is on average to obtain the mean value at pitch angle. As a result, through confirming, in each heat ray shielding material, particle pitch angle is in �� 30 ��.
Embodiment 11
-the UV-absorbing layer preparation of coating fluid 2-
Preparation has the UV-absorbing layer coating fluid 2 of following composition.
The UV-absorbing layer composition of coating fluid 2:
UV light absorber: Tinuvin326 (CibaJapan manufacture) 10 mass parts
Tackiness agent: polyvinyl alcohol solution 10 mass parts of 10 quality %
Water 30 mass parts
Use ball mill mixes these compositions and controls, so that volume average particle size is 0.6 ��m.
-formation of UV-absorbing layer-
Use line rod, in the way of the average dry thickness of coating can be 0.5 ��m, comprises the metallic particles of the heat ray shielding material of UV-absorbing layer coating fluid 2 paint embodiment 1 on layer. Then, at 100 DEG C to its heating 2 minutes, drying is also solidified, to form the UV-absorbing layer that also can serve as top coating.
Herein, the duplexer that stacking substrate/metallic particles comprises layer (comprising dull and stereotyped shape metallic particles)/UV-absorbing layer (also serving as top coating) successively is heat ray shielding film.
-formation of bonding coat-
The surface of thus obtained heat ray shielding film is cleaned, and cohesive bond layer thereon. As bonding coat (tackiness agent), it may also be useful to be the PET-W of Sanritz. Peeling off antiadhesion barrier from the side of PET-W, the UV-absorbing layer that then bonding film sticks to heat ray shielding film is on the surface.
According to said process, having obtained the heat ray shielding material of embodiment 11, its substrate/metallic particles comprising stacking successively comprises layer (comprising dull and stereotyped shape metallic particles)/UV-absorbing layer (also serving as top coating)/bonding coat.
Study the characteristic of the heat ray shielding material of thus obtained embodiment 11 according to the mode identical with embodiment 1, it has the trend identical with embodiment 1.
Industrial applicibility
The heat ray shielding material of the present invention has higher visible light transmissivity and higher solar reflectance, has excellent thermal shielding capability and has higher rub resistance, therefore can the arrangement wherein of dull and stereotyped shape metallic particles be kept. Therefore, this heat ray shielding material can effectively as the various parts needing to prevent invisible heat from passing through, such as, for the such as vehicle such as car, bus film and laminate structure, and buildings film and laminate structure, etc.
Reference numerals list
1 substrate
2 metallic particles comprise layer
2a metallic particles comprises the surface of layer
3 dull and stereotyped shape metallic particles
4 tops coating (preferably comprising UV light absorber)
10 heat ray shielding materials
11 bonding coats
D diameter
L thickness
The thickness of F (��) particle domain of the existence
Claims (12)
1. a heat ray shielding material, the metallic particles that described heat ray shielding material has the metallic particles comprising at least one type comprises layer, wherein, the thickness that described metallic particles comprises layer is 10nm��80nm, described metallic particles is to comprise hexagon to circular dull and stereotyped shape metallic particles relative to the total quantity of described metallic particles as the ratio of at least 60 number %, described hexagon to the mean thickness of circular dull and stereotyped shape metallic particles be 14nm at the most, and the domain of the existence thickness of described flat board shape metallic particles is 5nm��60nm.
2. heat ray shielding material as claimed in claim 1, wherein, described hexagon to the coefficient of variation of the leveled circular equivalent diameter of circular dull and stereotyped shape metallic particles is at the most 30%.
3. heat ray shielding material as claimed in claim 1, wherein, described hexagon is 70nm��500nm to the leveled circular equivalent diameter of circular dull and stereotyped shape metallic particles, and described hexagon is to the aspect ratio of circular dull and stereotyped shape metallic particles, i.e. average particulate diameter/average particle thickness is 6��40.
4. heat ray shielding material as claimed in claim 1, wherein, described hexagon at least comprises silver to circular dull and stereotyped shape metallic particles.
5. heat ray shielding material as according to any one of Claims 1 to 4, wherein, described hexagon to the principal plane of circular dull and stereotyped shape metallic particles comprises a surface of layer average 0 �㡫�� 30 �� of scope inner plane orientations relative to described metallic particles.
6. heat ray shielding material as according to any one of Claims 1 to 4, wherein, described metallic particles comprises layer and comprises polymkeric substance.
7. heat ray shielding material as claimed in claim 6, wherein, the principal polymeric that described metal comprises the described polymkeric substance comprised in layer is vibrin.
8. heat ray shielding material as according to any one of Claims 1 to 4, described heat ray shielding material has the layer comprising UV light absorber.
9. heat ray shielding material as claimed in claim 8, described heat ray shielding material has bonding coat, and wherein, the layer that described bonding coat or described bonding coat and described metallic particles comprise between layer comprises UV light absorber.
10. heat ray shielding material as according to any one of Claims 1 to 4, the visible light transmissivity of described heat ray shielding material is at least 70%.
The 11. heat ray shielding materials as according to any one of Claims 1 to 4, described heat ray shielding material reflect red outside line.
12. heat ray shielding materials as claimed in claim 1, wherein,
I thickness that () described metallic particles comprises layer is 30nm��80nm;
(ii) when the thickness that metallic particles is comprised layer is set to d, the described hexagon of at least 80 number % to circular dull and stereotyped shape metallic particles is present in from the surface that described metallic particles comprises layer in the scope of its d/2 degree of depth; And
(iii) described heat ray shielding material has substrate with the hexagon with at least 80 number % located in off-centered mode to the side that the face side of circular dull and stereotyped shape metallic particles is contrary what described metallic particles comprised layer.
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| JP2011-204199 | 2011-09-20 | ||
| JP2011204199 | 2011-09-20 | ||
| PCT/JP2012/074038 WO2013042718A1 (en) | 2011-09-20 | 2012-09-20 | Heat ray shielding material |
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| US (1) | US20140186608A1 (en) |
| EP (1) | EP2759854A4 (en) |
| JP (1) | JP5833518B2 (en) |
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| WO (1) | WO2013042718A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6097128B2 (en) * | 2013-04-12 | 2017-03-15 | 富士フイルム株式会社 | Far infrared light shielding layer forming composition |
| JP6301242B2 (en) * | 2014-11-28 | 2018-03-28 | 富士フイルム株式会社 | Infrared reflective pattern formation |
| DE102014226110A1 (en) * | 2014-12-16 | 2016-06-16 | Contitech Mgw Gmbh | Pipe and method of making a pipe |
| JP6649628B2 (en) * | 2016-12-09 | 2020-02-19 | トヨタ自動車株式会社 | Decorative coating |
| LU100018B1 (en) * | 2017-01-11 | 2018-08-14 | Luxembourg Inst Science & Tech List | Infrared reflective and electrical conductive composite film and manufacturing method thereof |
| DE112019001070B4 (en) * | 2018-03-29 | 2023-08-31 | Fujifilm Corporation | Wavelength selective absorbing material, infrared sensor, wavelength selective light source and radiation cooling system |
| US20240101861A1 (en) * | 2019-10-17 | 2024-03-28 | BASE Coatings GmbH | Nir light scattering coatings and compositions for preparing them |
| JP7443790B2 (en) * | 2020-01-30 | 2024-03-06 | コニカミノルタ株式会社 | Metallic silver-containing composition and method for producing metallic silver-containing composition |
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| JP2007178915A (en) * | 2005-12-28 | 2007-07-12 | Fujifilm Corp | Fine metal particle-dispersed material and infrared ray shielding filter |
| CN102050584A (en) * | 2009-11-06 | 2011-05-11 | 富士胶片株式会社 | Heat ray-shielding material |
| JP2011180562A (en) * | 2010-03-04 | 2011-09-15 | Konica Minolta Holdings Inc | Base material for shielding heat ray |
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| US6395398B1 (en) * | 1999-03-31 | 2002-05-28 | Central Glass Company, Limited | Frequency selective plate and method for producing same |
| JP3454422B2 (en) | 1999-07-16 | 2003-10-06 | セントラル硝子株式会社 | Radio wave transmitting wavelength selective substrate and its manufacturing method |
| US6649256B1 (en) * | 2000-01-24 | 2003-11-18 | General Electric Company | Article including particles oriented generally along an article surface and method for making |
| JP4855040B2 (en) * | 2005-10-14 | 2012-01-18 | 富士フイルム株式会社 | Infrared shielding filter |
| JP4881208B2 (en) | 2007-03-30 | 2012-02-22 | リンテック株式会社 | Solar radiation shielding film adhesive and solar radiation shielding film |
| US20100220388A1 (en) * | 2007-06-08 | 2010-09-02 | Bridgestone Corporation | Near-infrared shielding material, laminate including the same, and optical filter for display including the same |
| US8216704B2 (en) * | 2007-06-13 | 2012-07-10 | Teijin Limited | Biaxially oriented laminated film |
| EP2755065A4 (en) * | 2011-09-06 | 2015-06-10 | Fujifilm Corp | Heat ray shielding material |
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2012
- 2012-09-20 JP JP2012206996A patent/JP5833518B2/en not_active Expired - Fee Related
- 2012-09-20 CN CN201280045500.6A patent/CN103814310B/en not_active Expired - Fee Related
- 2012-09-20 WO PCT/JP2012/074038 patent/WO2013042718A1/en active Application Filing
- 2012-09-20 EP EP12833192.3A patent/EP2759854A4/en not_active Withdrawn
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2014
- 2014-03-04 US US14/196,177 patent/US20140186608A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007178915A (en) * | 2005-12-28 | 2007-07-12 | Fujifilm Corp | Fine metal particle-dispersed material and infrared ray shielding filter |
| CN102050584A (en) * | 2009-11-06 | 2011-05-11 | 富士胶片株式会社 | Heat ray-shielding material |
| JP2011180562A (en) * | 2010-03-04 | 2011-09-15 | Konica Minolta Holdings Inc | Base material for shielding heat ray |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2759854A1 (en) | 2014-07-30 |
| US20140186608A1 (en) | 2014-07-03 |
| JP5833518B2 (en) | 2015-12-16 |
| WO2013042718A1 (en) | 2013-03-28 |
| CN103814310A (en) | 2014-05-21 |
| EP2759854A4 (en) | 2015-04-22 |
| JP2013080222A (en) | 2013-05-02 |
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